Hydrochloric Acid → 2-(2,3-Difluoro-4-trimethylsilylphenyl)-5,5-dimethyl-1,3,2-dioxaborinane

HRID 1645456Notes

Reaction equation

HRID 1645456 reaction equation
[Li]C[CH2:3][CH2:4][CH3:5].[F:6][C:7]1[CH:12]=[CH:11][CH:10]=[C:9]([Si:13]([CH3:16])([CH3:15])[CH3:14])[C:8]=1[F:17].[B:18](OC(C)C)([O:23][CH:24](C)C)[O:19][CH:20](C)C.Cl.OCC(C)(CO)C.S([O-])([O-])(=O)=O.[Mg+2]>O1CCCC1.C(OC)(C)(C)C.O>[F:6][C:7]1[C:8]([F:17])=[C:9]([Si:13]([CH3:14])([CH3:16])[CH3:15])[CH:10]=[CH:11][C:12]=1[B:18]1[O:23][CH2:24][C:4]([CH3:3])([CH3:5])[CH2:20][O:19]1

Participants

10

Reactant 6

HCID 313Hydrochloric AcidHCID 21531Triisopropyl borateHCID 24083Sulfuric acid magnesium salt (1:1)HCID 31344Neopentyl glycolHCID 108993711,2-Difluoro-3-trimethylsilylbenzeneHCID 178418339Butyllithium

Product 1

HCID 108918462-(2,3-Difluoro-4-trimethylsilylphenyl)-5,5-dimethyl-1,3,2-dioxaborinane

Reagents, catalysts & solvents 3

HCID 962WaterSolventHCID 8028TetrahydrofuranSolventHCID 15413tert-Butyl methyl etherSolvent

Procedure

625 ml (1 mol) of 1.6 M BuLi are added dropwise at −78° C. to a solution of 169 g (910 mmol) of 1,2-difluoro-3-trimethylsilylbenzene (5) in 1.4 l of dry tetrahydrofuran. After 15 minutes, 276 ml (1.2 mol) of triisopropyl borate are added dropwise. The mixture is allowed to warm to room temperature overnight 200 ml of water, 200 ml of methyl tert-butyl ether and 100 ml of conc. HCl are subsequently added. The organic phase is washed with water (2×100 ml) and sat. NaCl (1×100 ml) and dried using magnesium sulfate, and the solvent is removed under reduced pressure. The oily residue is dissolved in 270 ml of THF, and 94 g (910 mmol) of neopentyl glycol and 455 g of magnesium sulfate are added. After the mixture has been stirred for 1 hour, the solvent is removed under reduced pressure, and petroleum ether (273 ml) is added to the oily residue. Precipitated neopentyl glycol is removed by filtration. 251 g (87%) of 6 crystallise from the filtrate at −25° C.

Workup

  1. additionare subsequently added
  2. washThe organic phase is washed with water (2×100 ml) and sat. NaCl (1×100 ml)
  3. customdried
  4. customthe solvent is removed under reduced pressure
  5. dissolutionThe oily residue is dissolved in 270 ml of THF
  6. customthe solvent is removed under reduced pressure, and petroleum ether (273 ml)
  7. additionis added to the oily residue
  8. customPrecipitated neopentyl glycol is removed by filtration
  9. custom251 g (87%) of 6 crystallise from the filtrate at −25° C.

Sources & evidence

ORD record
ord-bc3b70cdbd1a45c8bc3ffe06d0c041ca
Source dataset
uspto-grants-2012_02
Patent number
US08124817B2

Reaction notes

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